Processes for producing polyacrylonitrile-base precursor fibers and carbon fibers

ABSTRACT

A process for producing polyacrylonitrile-base precursor fibers for production of carbon fibers, which comprises spinning a spinning dope containing 10 to 25 wt % of a polyacrylonitrile-base polymer having an intrinsic viscosity of 2.0 to 10.0 by extruding the spinning dope from a spinneret by a wet spinning or a dry wet spinning method, drying and heat-treating fibers obtained by the spinning, and then steam drawing the resulting fibers, wherein the linear extrusion rate of the polyacrylonitrile-base polymer from the spinneret is 2 to 15 m/min.

RELATED APPLICATIONS

This is a divisional of U.S. Ser. No. 12/097,277, filed Jun. 13, 2008,which is a §371 of International Application No. PCT/JP2006/324343, withan international filing date of Dec. 6, 2006 (WO 2007/069511 A1,published Jun. 21, 2007), which is based on Japanese Patent ApplicationNo. 2005-359049, filed Dec. 13, 2005.

TECHNICAL FIELD

This disclosure relates to carbon fibers excellent in compressivestrength and tensile elastic modulus and a process for producing thesame. Further, the disclosure relates to a process for producingpolyacrylonitrile-base precursor fibers used for production of thecarbon fibers.

BACKGROUND

Carbon fibers are used in various applications owing to their excellentmechanical properties and electric properties. The conventionalapplications of carbon fibers include sporting goods such as golf clubsand fishing rods and aircraft, and in recent years, in addition, carbonfibers are increasingly used in so-called general industrialapplications as automobile members, compressed natural gas (CNG) tanks,aseismic reinforcing members of buildings and ship members. Thistendency requires higher levels of mechanical properties. For example,in the aircraft application, many of the structural members are beingreplaced by carbon fiber reinforced plastics lighter in weight, andcarbon fibers having both high compressive strength and high tensileelastic modulus are being demanded.

The industrial production of carbon fibers undergoes a stabilizationstep of heat-treating precursor fibers made of a polymer such aspolyacrylonitrile in air with a temperature of 200 to 300° C. and acarbonization step of heat-treating the stabilized fibers obtained inthe stabilization step in an inert atmosphere with a temperature of 300to 3,000° C. In general, if the highest temperature in the carbonizationstep is higher, the tensile elastic modulus of the obtained carbonfibers can be made higher, but since graphite crystals grow, thecompressive strength of the obtained carbon fibers decline. That is,there is trade-off relation between the tensile elastic modulus and thecompressive strength of carbon fibers. To overcome the trade-offrelation, several techniques for enhancing the compressive strength andthe tensile elastic modulus have been proposed in addition to those forcontrolling the carbonization temperature.

Techniques proposed for enhancing the compressive strength of carbonfibers include, for example, a technique of implanting ions into carbonfibers, for making graphite crystals amorphous and a technique of usingprecursor fibers with a noncircular cross sectional form for increasingthe geometrical moment of inertia (see JP 3-180514 A and JP 3-185121 A).However, the former proposal allows carbon fibers to be treated onlylittle by little in high vacuum, and the latter proposal has a problemin view of uniformity of final products, since it is difficult tomaintain the sectional form stably. Both the proposals involvedifficulty in industrial application.

To enhance the tensile elastic modulus of carbon fibers, as is known, itis effective to draw fibers at the time of stabilizing-carbonizingtreatment, for enhancing the orientation degree of carbon fibers.However, merely enhancing the draw ratio causes fuzz generation andfiber breakage, and it cannot be avoided that the production stabilityand the grade of the obtained carbon fibers decline. Techniques forstabilizing drawing by controlling stabilizing-carbonizing treatmentconditions are also proposed (see JP 2004-91961 A and JP 2004-197278 A).However, the drawing level achieved is not satisfactorily high, whilethe effect of enhancing the tensile elastic modulus by drawing isslight.

A technique for enhancing oxygen permeability of the precursor fibers tobe used and homogenizing reaction among the single filaments in thestabilization step, to thereby enhancing the tensile elastic modulus ofthe obtained carbon fibers, is proposed (see JP 2-84505 A). However,this proposal has a problem that, since as much as more than 1.5% of acomonomer is used for enhancing the oxygen permeability, the heatresistance of the precursor fibers declines, though the effect ofenhancing the tensile elastic modulus can be certainly obtained. Thedecline of heat resistance causes more single filaments to adhere toeach other in the drying heat treatment step or the steam drawing stepof the fiber producing step, and in the stabilizing or carbonizing inthe stabilizing-carbonizing treatment step, to lower the productionstability and the tensile strength and compressive strength of theobtained carbon fibers.

It could therefore be helpful to provide carbon fibers excellent in bothcompressive strength and tensile elastic modulus without impairingproductivity and processability, and also to provide a productionprocess thereof. It could also be helpful to-provide a process forproducing polyacrylonitrile-base precursor fibers used for production ofthe carbon fibers.

We obtain carbon fibers by spinning a polyacrylonitrile-base polymer andsubsequently using a stabilizing-carbonizing treatment so that thecarbon fibers have a strand tensile modulus of 320 to 380 GPa and aconduction electron density of 3.0×10¹⁹ to 7.0×10¹⁹ spins/g asdetermined by electron spin resonance.

In the carbon fibers, it is preferred that the strand tensile modulus is330 to 380 GPa and that the conduction electron density as determined byelectron spin resonance is 4.0×10¹⁹ to 7.0×10¹⁹ spins/g.

In the carbon fibers, it is preferred that the crystal size of thecarbon fibers is 1.8 to 2.6 nm.

In the carbon fibers, it is preferred that the specific gravity of thecarbon fibers is 1.75 to 1.85.

In the carbon fibers, it is preferred that the average single filamentdiameter of the carbon fibers is 4.5 to 7.5

The process for producing polyacrylonitrile-base precursor fibers forproduction of carbon fibers for achieving the abovementioned objects,which comprises spinning a spinning dope containing 10 to 25 wt % of apolyacrylonitrile-base polymer having an intrinsic viscosity of 2.0 to10.0 by extruding it from a spinneret by a wet spinning or dry wetspinning method, drying and heat-treating the fibers obtained in thespinning step, and steam-drawing the fibers obtained, wherein the linearextrusion rate of the polyacrylonitrile-base polymer from the spinneretis 2 to 15 m/min.

In the process for producing polyacrylonitrile-base precursor fibers forproduction of carbon fibers, it is preferred that the linear extrusionrate is 2 to 10 in/min.

In the process for producing polyacrylonitrile-base precursor fibers forproduction of carbon fibers, it is preferred that the spinning method isa dry wet spinning method.

In the process for producing polyacrylonitrile-base precursor fibers forproduction of carbon fibers, it is preferred that the melting point Tmin wet heat of the polyacrylonitrile-base polymer measured by adifferential scanning calorimeter is 186 to 200° C.

In the process for producing polyacrylonitrile-base precursor fibers forproduction of carbon fibers, it is preferred that thepolyacrylonitrile-base polymer is a copolymer containing a componentcopolymerizable with acrylonitrile and that the amount of thecopolymerizable component is 0.1 to 0.5 mol %.

In the process for producing polyacrylonitrile-base precursor fibers forproduction of carbon fibers, it is preferred that the single filamentfineness of the polyacrylonitrile-base precursor fibers for productionof carbon fibers is 0.7 to 1.0 dtex.

The process for producing carbon fibers comprises stabilizing thepolyacrylonitrile-base precursor fibers for production of carbon fibers,produced by the process for producing polyacrylonitrile-base precursorfibers for production of carbon fibers, in air with a temperature of 200to 300° C., while drawing them at a draw ratio of 0.80 to 1.20,preliminarily carbonizing the fibers obtained in an inert atmospherewith a temperature of 300 to 800° C., while drawing them at a draw ratioof 1.00 to 1.30, and carbonizing the fibers obtained in an inertatmosphere with a temperature of 1,000 to 2,000° C., while drawing themat a draw ratio of 0.96 to 1.05.

In the process for producing carbon fibers, it is preferred that thedraw ratio in the stabilization step is 0.90 to 1.20, that the drawratio in the preliminary carbonization step is 1.10 to 1.30, and thatthe draw ratio in the carbonization step is 0.97 to 1.05.

If the polyacrylonitrile-base precursor fibers for production of carbonfibers, produced by the process for producing polyacrylonitrile-baseprecursor fibers for production of carbon fibers are used, fibers can bedrawn highly and stably in the carbon fiber production process withoutimpairing the productivity and processability of the carbon fiberproduction process. As a result, carbon fibers excellent in compressivestrength and tensile modulus, and excellent further in tensile strengthand grade can be produced at low cost.

DETAILED DESCRIPTION

We found that the polyacrylonitrile-base precursor fibers for productionof carbon fibers, produced by extruding, for spinning, a spinning dopecontaining a polyacrylonitrile-base polymer with its intrinsic viscositykept in a specific range at any polymer concentration in a specificrange, from a spinneret at any linear extrusion rate in a specificrange, can be highly drawn in the stabilizing-carbonizing treatment stepfor producing carbon fibers.

We found that the breakage of fibers at the time of drawing in thestabilizing-carbonizing treatment step for producing carbon fibers canbe inhibited, first by enhancing the intrinsic viscosity, namely,raising the molecular weight, to thereby make the molecular chainslonger while intensifying the inter-molecular connections in the fiberaxis direction, second by controlling the polyacrylonitrile-base polymerconcentration of the spinning dope, to intensify the inter-molecularentanglement, namely, the inter-molecular connections, and third bycontrolling the linear extrusion rate of the spinning dope from thespinneret, to form fibers from the spinning dope without loosening theinter-molecular entanglement.

Further, we found that, if the strand tensile modulus and the conductionelectron density determined by electron spin resonance are controlled inspecific ranges, carbon fibers having both a high level of tensilemodulus and a high level of compressive strength can be obtained. Thecarbon fibers can be obtained by stabilizing-carbonizing treatment ofthe fibers obtained by spinning a polyacrylonitrile-base polymer. Theobtained carbon fibers have a strand tensile modulus of 320 to 380 GPaand a conduction electron density of 3.0×10¹⁹ to 7.0×10¹⁹ spins/g asdetermined by electron spin resonance (hereinafter may be abbreviated asESR).

It is highly preferred that the strand tensile modulus of carbon fibersis 320 to 380 GPa. A more preferred strand tensile modulus range is 330to 380 GPa. A further more preferred strand tensile modulus range is 340to 370 GPa. It is preferred that the strand tensile modulus of carbonfibers is higher, since the tensile modulus and the compressive modulusof the obtained composite can be enhanced. If the strand tensile modulusis smaller than 320 GPa, it is difficult to apply the carbon fibers to aregion where stiffness is required in aircraft application, etc. On theother hand, the carbon fibers with a strand tensile modulus of higherthan 380 GPa are difficult to produce even if the process for producingcarbon fibers of the invention is applied.

The strand tensile modulus can be controlled mainly by the carbonizationtemperature of precursor fibers and the draw ratio at the time ofstabilizing-carbonizing treatment. If the carbonization temperature ishigher, the strand tensile modulus can be made higher, but it should benoted that since the crystal size of carbon fibers becomes largesimultaneously, it is difficult to exhibit high compressive strength.For enhancing the strand tensile modulus while controlling the crystalsize of carbon fibers in a specific range, how to enhance the draw ratioat the time of stabilizing-carbonizing treatment is important.

It is highly preferred that the carbon fibers have a conduction electrondensity of 3.0×10¹⁹ to 7.0×10¹⁹ spins/g as determined by electron spinresonance (ESR). A more preferred conduction electron density range is4.0×10¹⁹ to 7.0×10¹⁹ spins/g, and a further more preferred conductionelectron density range is 4.2×10¹⁹ to 6.6×10¹⁹ spins/g. The conductionelectron density measured by ESR corresponds to the amount of conjugatedbonds in the crystals of carbon fibers and, if this value is higher, thegraphite network faces develop well to reflect high two-dimensionality.

Compared with the conventional carbon fibers having a strand tensilemodulus of 320 to 380 GPa, the carbon fibers are characteristically lowin the conduction electron density and high in three-dimensionality.Since the high three-dimensionality inhibits the microbuckling failureof graphite crystals at the time of compression, the compressivestrength of carbon fibers can be enhanced. If the conduction electrondensity is lower than 3.0×10¹⁹ spins/g, two-dimensionality declines somuch as to lower the strand tensile modulus. Further, if the conductionelectron density is higher than 7.0×10¹⁹ spins/g, three-dimensionalitydeclines so much as not to provide a clear effect of enhancing thecompressive strength of carbon fibers.

The conduction electron density can be controlled by the molecularweight of the polyacrylonitrile-base polymer used for producing thepolyacrylonitrile-base precursor fibers for production of carbon fibers,the polymer concentration of the spinning dope, the linear extrusionrate of the spinning dope extruded from the spinneret, further thecarbonization temperature for stabilizing-carbonizing treatment of thepolyacrylonitrile-base precursor fibers for production of carbon fibers,for producing carbon fibers.

The conduction electron density can be lowered by enhancing themolecular weight of the polyacrylonitrile-base polymer and the polymerconcentration and lowering the linear extrusion rate. Further, theconduction electron density can also be lowered by enhancing thecarbonization temperature. However, as described before, if thecarbonization temperature is changed, the strand tensile modulus ofcarbon fibers and the crystal size of carbon fibers are also changed.For obtaining the carbon fibers, it is important to control theconduction electron density by any other method than changing thecarbonization temperature.

It is preferred that the crystal size of the carbon fibers is 1.8 to 2.6nm. A more preferred range is 1.9 to 2.5 nm, and a further morepreferred range is 2.0 to 2.4 nm. If the crystal size of carbon fibersis smaller than 1.8 nm, a high strand tensile modulus may be unlikely tobe exhibited. Further, if the crystal size of carbon fibers is largerthan 2.6 nm, there arises a problem that the compressive strengthdeclines. The crystal size of carbon fibers can be controlled by thecarbonization temperature.

It is preferred that the specific gravity of the carbon fibers is 1.75to 1.85. If the specific gravity of carbon fibers is lower than 1.75,the crystal structure of carbon fibers is insufficiently densified, andthe strand tensile modulus is unlikely to be enhanced. Further, if thespecific gravity is higher than 1.85, the crystal structure of carbonfibers becomes close to that of graphite, and there arises a problemthat the compressive strength declines. The specific gravity can becontrolled by adjusting the stabilization treatment time, the draw ratioin the stabilizing-carbonizing treatment step, the temperature risingrates in the preliminary carbonization step and the carbonization step,the temperature of the carbonization step, etc.

It is preferred that the average single filament diameter of the carbonfibers is 4.5 to 7.5 μm. If the average single filament diameter issmaller than 4.5 μm, there arises a problem that productivity declinesdue to single filament breakage during spinning and drawing. Further, ifthe average single filament diameter is larger than 7.5 μm, there arisesa problem that the strand tensile modulus cannot be enhanced since thestabilization treatment inside the single filaments is insufficient. Apreferred average single filament diameter range is 4.7 to 6.0 μm.

Next, the process for producing polyacrylonitrile-base precursor fibersfor production of carbon fibers is explained below.

It is preferred that the polyacrylonitrile-base polymer used in thepolyacrylonitrile-base precursor fibers for production of carbon fibershas an acrylonitrile content of at least 95 mol % or more and anintrinsic viscosity of 2.0 to 10.0. A more preferred intrinsic viscosityrange is 2.3 to 8.0 and a further more preferred intrinsic viscosityrange is 2.5 to 6.0.

In the case of a low molecular weight polyacrylonitrile-base polymerhaving an intrinsic viscosity of lower than 2.0, since theinter-molecular connections in the fiber axis direction decline, theability to enhance drawability in the stabilizing-carbonizing treatmentstep decreases. Further, though a higher intrinsic viscosity ispreferred, it is virtually difficult to obtain a high molecular weightpolyacrylonitrile-base polymer having an intrinsic viscosity of higherthan 10.0, since the spinning dope is remarkably gelled. The intrinsicviscosity of the polyacrylonitrile-base polymer can be controlled bychanging the amounts of the monomer to be polymerized, initiator, chaintransfer agent, etc.

It is preferred that the melting point Tm in wet heat of thepolyacrylonitrile-base polymer, as measured by a differential scanningcalorimeter (hereinafter may be abbreviated as

DSC), is 186 to 200° C. A more preferred range is 188 to 198° C., and afurther more preferred range is 190 to 195° C. If the melting point Tmin wet heat is lower than 186° C., the coalescence between singlefilaments becomes remarkable and, as a result, it may become difficultto enhance drawability in the stabilizing-carbonizing treatment step.Further, if the melting point Tm in wet heat is higher than 200° C.,steam of higher temperature, namely, steam of higher pressure isrequired for steam drawing, and the high pressure breaks fibersremarkably. Therefore, as a result, productivity may decline, and thegrade and mechanical properties of the obtained carbon fibers maydecline.

The melting point Tm in wet heat can be controlled by the comonomer usedin the mainly used polyacrylonitrile-base polymer, the copolymerizedamount of it, etc. In general, the melting point Tm in wet heat tends todecline when the copolymerized amount of the comonomer is larger, andthe degree of decline is different from comonomer to comonomer. It ispreferred that the copolymerized amount of the comonomer is 0.5 mol % orless. More preferred is 0.4 mol % or less, and further more preferred is0.3 mol % or less. For the purpose of expediting the stabilizationreaction, it is preferred to copolymerize at least 0.1 mol % or more ofa stabilization accelerator as the comonomer.

As the stabilization accelerator, for example, a compound having one ormore carboxyl groups or amide groups can be preferably used. It ispreferred for the purpose of enhancing productivity that thecopolymerized amount of the stabilization accelerator is larger, sincethe stabilization reaction can be accelerated to allow the stabilizationtreatment to be completed in a shorter time. However, on the other hand,if the copolymerized amount of the stabilization accelerator is larger,the melting point Tm in wet heat declines and the heating rate becomeslarge, threatening that runaway reaction may occur. Therefore, it ispreferred that the copolymerized amount is not more than 0.5 mol %. Amore preferred copolymerized amount range is 0.1 to 0.4 mol %, and afurther more preferred range is 0.1 to 0.3 mol %.

Particular examples of the stabilization accelerator as a comonomerinclude acrylic acid, methacrylic acid, itaconic acid, crotonic acid,citraconic acid, ethacrylic acid, maleic acid, mesaconic acid,acrylamide and methacrylamide. For the purpose of preventing the declineof the melting point Tm in wet heat, it is preferred to use a smallamount of a monomer having a high stabilization acceleration effect, andit is preferred to use a stabilization accelerator having a carboxylgroup rather than an amide group.

Further, it is more preferred that the number of the amide groups orcarboxyl groups contained is two or more rather than one, and from thispoint of view, as the stabilization accelerator used as a comonomer,acrylic acid, methacrylic acid, itaconic acid, crotonic acid, citraconicacid, ethacrylic acid, maleic acid or mesaconic acid is preferred.Itaconic acid, maleic acid or mesaconic acid is more preferred, andabove all, itaconic acid is most preferred.

For the purpose of enhancing spinnability and drawability, a comonomerother than the stabilization accelerator, such as an acrylate ormethacrylate, can also be copolymerized. However, for the purpose ofpreventing the decline of the melting point Tm in wet heat, it ispreferred that the total amount of the comonomers other thanacrylonitrile is not more than 0.5 mol %. More preferred is not morethan 0.4 mol %, and further more preferred is not more than 0.3 mol %.

The polymerization method used for producing the polyacrylonitrile-basepolymer can be selected from publicly known polymerization methods suchas solution polymerization, suspension polymerization and emulsionpolymerization. For the purpose of homogeneously polymerizingcomonomers, it is preferred to use solution. polymerization.

As the solution used for solution polymerization, it is preferred to usea solvent capable of dissolving polyacrylonitrile, such as dimethylsulfoxide, dimethylformamide or dimethylacetamide. Among them in view ofsolubility, dimethyl sulfoxide can be preferably used.

The polyacrylonitrile-base precursor fibers for production of carbonfibers can be produced by using the aforementionedpolyacrylonitrile-base polymer. The polyacrylonitrile-base polymer isdissolved in a solvent capable of dissolving polyacrylonitrile, such asdimethyl sulfoxide, dimethylformamide or dimethylacetamide, to prepare aspinning dope. In the case where solution polymerization is used, if thesolvent used for polymerization is the same as the solvent used forspinning (spinning solvent), the step of separating the obtainedpolyacrylonitrile-base polymer and re-dissolving it into a spinningsolvent is not necessary.

It is highly preferred that the concentration of thepolyacrylonitrile-base polymer in the spinning dope is 10 to 25 wt %. Apreferred concentration range is 12 to 23 wt %, and a more preferredrange is 14 to 21 wt %. If the polymer concentration is less than 10 wt%, the inter-molecular entanglement in the spinning dope declines toweaken the inter-molecular connections in the radial directions of thepolyacrylonitrile-base precursor fibers for production of carbon fibers,obtained by spinning, and the ability to enhance drawability in thestabilizing-carbonizing treatment step cannot be obtained. It ispreferred that the polymer concentration is higher, since theaforementioned inter-molecular entanglement can be intensified, but ifthe concentration is higher than 25 wt %, the spinning dope is gelledremarkably, making stable spinning difficult. The polymer concentrationcan be controlled by adjusting the rate of the spinning solvent to thepolyacrylonitrile-base polymer.

For obtaining carbon fibers having high strength, it is preferred to letthe spinning dope pass through a filter having 1μm or smaller meshesbefore spinning, to remove the impurities straying into the rawmaterials of the polyacrylonitrile-base polymer or processed materialsin the respective steps of the process.

The spinning dope is extruded from a spinneret by a wet spinning methodor dry wet spinning method, and introduced into a coagulation bath, tobe coagulated, for forming polyacrylonitrile-base precursor fibers forproduction of carbon fibers. For the purpose of enhancing the densenessof the obtained polyacrylonitrile-base precursor fibers for productionof carbon fibers and for the purpose of enhancing the mechanicalproperties of the obtained carbon fibers, a dry wet spinning method ofextruding the spinning dope once into air and then introducing it intothe coagulation bath is more preferred than a wet spinning method ofdirectly extruding the spinning dope into the coagulation bath.

It is highly preferred that the linear extrusion rate for extruding thespinning dope from the spinneret is 2 to 15 in/min. A preferred linearextrusion rate range is 2 to 10 in/min, and a more preferred range is 4to 8 m/min.

For the purpose of enhancing the drawability in thestabilizing-carbonizing treatment step of the polyacrylonitrile-baseprecursor fibers for production of carbon fibers, a lower linearextrusion rate is preferred. If the linear extrusion rate is higher than15 in/min, a clear effect of enhancing the drawability in thestabilizing-carbonizing treatment step cannot be obtained. Further, ifthe linear extrusion rate is lowered, the stability at the time ofextrusion declines, and fineness variation, fiber breakage, etc. arelikely to occur. If the linear extrusion rate is lower than 2 m/min,stable spinning and drawing are difficult.

The reason why the drawability in the stabilizing-carbonizing treatmentstep can be enhanced by controlling the linear extrusion rate in aspecific range is not clear, but is estimated to be as follows. If thelinear extrusion rate is lowered, the shear rate at the extrusion holesof the spinneret at the time of extrusion declines, and it is consideredthat accordingly the loosening of entanglement by the shear at the timeof extrusion can be inhibited. Therefore, it is considered that, if theintrinsic viscosity and the polymer concentration are controlled in theaforementioned specific ranges, the state of moderate inter-molecularentanglement is reflected as it is in the fiber structure, without beinggreatly changed by extrusion. It is considered that, if the fibersformed of the polyacrylonitrile-base polymer having moderateinter-molecular entanglement are used as precursor fibers, theinter-molecular and inter-crystalline connections can be developed inthe stabilizing-carbonizing treatment step to enhance the drawability inthe stabilizing-carbonizing treatment step.

Techniques for enhancing the processability during spinning and drawingand enhancing the tensile strength of the obtained carbon fibers bycontrolling the draft, namely, the ratio between the linear extrusionrate and the take-up speed in a specific range are known. However, wefound that the control of the state before extrusion is more effectivethan the control of the state after extrusion such as the control ofdraft, for solving the problem of enhancing the drawability in thestabilizing-carbonizing treatment step.

If the amount of the spinning dope extruded from the spinneret is A(ml/min), the diameter of the extrusion holes of the spinneret is d(mm), and the number of extrusion holes is n, then the linear extrusionrate can be defined as follows:

Linear extrusion rate (m/min)=A/((d/2)² ×π×n)×1,000.

Therefore, in the case where a polyacrylonitrile-base precursor fiberbundle comprising a certain number of filaments for production of carbonfibers is produced, the linear extrusion rate can be set at an arbitraryvalue by changing the extrusion amount and/or changing the diameter ofthe extrusion holes. Since the adjustment of extrusion amount may affectthe single filament fineness of the obtained polyacrylonitrile-baseprecursor fibers for production of carbon fibers and the productivity ofspinning and drawing equipment, it is more preferred to set anappropriate diameter of extrusion holes for adaptation to the necessaryextrusion amount.

It is preferred that the coagulation bath used in the spinning stepcontains a solvent used as the solvent of the spinning dope such asdimethyl sulfoxide, dimethylformamide or dimethylacetamide, and aso-called “coagulation accelerator.” As the coagulation accelerator, acompound incapable of dissolving the polyacrylonitrile-base polymer andcompatible with the solvent used in the spinning dope can be used.Particularly it is preferred to use water as the coagulationaccelerator.

A fiber bundle comprising numerous filaments spun from the spinneret isintroduced into the coagulation bath, to coagulate the respectivefilaments, and the coagulated filaments undergo a water washing step,bath drawing step, oiling step, drying heat treatment step and steamdrawing step, to obtain polyacrylonitrile-base precursor fibers forproduction of carbon fibers.

The fiber bundle derived from the coagulation bath can also be directlyintroduced into the bath drawing step, omitting the water washing step,or after the solvent is removed in the water washing step, the fiberbundle free from the solvent can be introduced into the bath drawingstep. It is preferred that the bath drawing is performed in a singledrawing bath or multiple drawing baths usually kept at a temperature of30 to 98° C. A preferred draw ratio range is 1 to 5. times, and a morepreferred range is 2 to 4.

After completion of the bath drawing step, for the purpose of preventingthe coalescence between single filaments, it is preferred to apply anoil agent composed of a silicone, etc. to the fiber bundle. As thesilicone oil agent, it is preferred to use a modified silicone. As thesilicone oil agent, an oil agent containing an amino modified siliconewith high heat resistance can be used.

It is preferred that the temperature of drying heat treatment is 160 to200° C. A more preferred range is 165 to 198° C., and a further morepreferred range is 175 to 195° C. If the temperature of drying heattreatment is lower than 160° C., the denseness of the obtainedpolyacrylonitrile-base precursor fibers for production of carbon fibersis insufficient, and it may be difficult to obtain the effects. Further,if the temperature of the drying heat treatment is higher than 200° C.,the coalescence between single filaments is remarkable, and the tensilestrength of the obtained carbon fibers may decline.

For the drying heat treatment, the fiber bundle may be allowed to run incontact with a heated roller or may also be allowed to run in a heatedatmosphere, but in view of drying efficiency, it is preferred that thefiber bundle is allowed to run in contact with a heated roller.

The steam drawing is performed to draw the fiber bundle in pressuresteam preferably to 3 times or more, more preferably to 4 times or more,further more preferably to 5 times or more. It is preferred that thetotal draw ratio in the water washing step, bath drawing step and steamdrawing step as a whole is 8 to 15 times for the purpose of enhancingthe mechanical properties of the obtained carbon fibers. A morepreferred total draw ratio range is 10 to 14.5 times, and a further morepreferred range is 11 to 14 times. If the total draw ratio is lower than8 times, the orientation degree of the obtained polyacrylonitrile-baseprecursor fibers for production of carbon fibers declines, and highdrawability cannot be obtained in the subsequent stabilizing-carbonizingtreatment step for producing carbon fibers. Further, if the total drawratio is higher than 15 times, the filament breakage during drawingoccurs frequently, to lower the grade of the obtainedpolyacrylonitrile-base precursor fibers for production of carbon fibersand the obtained carbon fibers.

It is preferred that the single filament fineness of thepolyacrylonitrile-base precursor fibers for production of carbon fibersis 0.7 to 1.0 dtex. If the single filament fineness is smaller than 0.7dtex, the spinnability during spinning and drawing declines to lower theproduction stability, and the productivity per the number of extrusionholes declines to greatly raise the cost. On the other hand, if thesingle filament fineness is larger than 1.0 dtex, the structuraldifference between the inner and outer layers of each of the filamentsforming the obtained stabilized fiber bundle becomes remarkable, and thetensile strength and the strand tensile modulus of the obtained carbonfibers may decline.

It is preferred that the number of filaments forming thepolyacrylonitrile-base precursor fiber bundle for production of carbonfibers is 1,000 to 3,000,000. A more preferred range is 6,000 to3,000,000, and a further more preferred range is 12,000 to 2,500,000.The most preferred range is 24,000 to 2,000,000. For the purpose ofenhancing productivity, it is preferred that the number of filaments,which is 1,000 or larger, is as large as possible. However, if thenumber of filaments is larger than 3,000,000, stabilization treatmentmay not be able to uniformly reach inside the polyacrylonitrile-baseprecursor fiber bundle for production of carbon fibers.

Next, the process for producing carbon fibers is explained below.

The carbon fibers can be produced by stabilizing thepolyacrylonitrile-base precursor fibers for, production of carbonfibers, produced by the process for producing polyacrylonitrile-baseprecursor fibers for production of carbon fibers, in air having atemperature of 200 to 300° C., while drawing at a draw ratio of 0.80 to1.20, subsequently preliminarily carbonizing in an inert atmospherehaving a temperature of 300 to 800° C., while drawing at a draw ratio of1.00 to 1.30, and carbonizing in an inert atmosphere having atemperature of 1,000 to 2,000° C., while drawing at a draw ratio of 0.96to 1.05.

It is preferred that the draw ratio for stabilization is 0.80 to 1.20. Amore preferred range is 0.90 to 1.20, and a further more preferred rangeis 0.85 to 1.10. if the draw ratio is lower than 0.80, the orientationdegree of the obtained stabilized fibers is insufficient, and the strandtensile modulus of the obtained carbon fibers may decline: Further, ifthe draw ratio is higher than 1.20, the processability may decline dueto fuzz generation and fiber breakage.

The stabilization treatment time can be appropriately selected in arange from 10 to 100 minutes. For the purpose of enhancing theprocessability of the subsequent preliminary carbonization and for thepurpose of enhancing the mechanical properties of the obtained carbonfibers, it is preferred to set the time for ensuring that the specificgravity of the obtained stabilized fibers can be kept in a range from1.3 to 1.38.

The preliminary carbonization and carbonization are performed in aninert atmosphere, and the inert gas used can be, for example, nitrogen,argon or xenon, etc. In view of economy, nitrogen can be preferablyused.

It is preferred that the temperature of preliminary carbonization is 300to 800° C., and that the temperature rising rate in the preliminarycarbonization is set at 500° C./min or less.

It is preferred that the draw ratio in the preliminary carbonization is1.00 to 1.30. A more preferred range is 1.10 to 1.30, and a further morepreferred range is 1.10 to 1.20. If the draw ratio is lower than 1.00,the orientation degree of the obtained preliminarily carbonized fibersis insufficient, and the strand tensile modulus of the carbon fibers maydecline. Further, if the drawing ratio is higher than 1.30, theprocessability may decline due to fuzz generation and fiber breakage.

It is preferred that the temperature of carbonization is 1,000 to 2,000°C. A more preferred range is 1,200 to 1,800° C., and a further morepreferred range is 1,300 to 1,600° C. If the highest temperature ofcarbonization is higher, the strand tensile modulus is higher, but sincegraphitization takes place to increase the crystal size, the compressivestrength may decline as a result. So, the temperature of carbonizationshould be set considering the balance between strand tensile modulus andcompressive strength.

It is preferred that the draw ratio for carbonization is 0.96 to 1.05. Amore preferred range is 0.97 to 1.05, and a further more preferred rangeis 0.98 to 1.03. If the draw ratio is lower than 0.96, the orientationdegree and denseness of the obtained carbon fibers become insufficient,and the strand tensile modulus may decline. Further, if the draw ratiois higher than 1.05, the processability may decline due to fuzzgeneration and fiber breakage.

The obtained carbon fibers may also be treated by electrolysis, to bemodified on the surfaces. The electrolyte used for the electrolytictreatment can be an acid solution of sulfuric acid, nitric acid orhydrochloric acid, or an aqueous solution of an alkali such as sodiumhydroxide, potassium hydroxide, tetraethylammonium hydroxide, ammoniumcarbonate or ammonium bicarbonate or any of their salts. The quantity ofelectricity used for the electrolytic treatment can be selected asrequired in response to the carbonization degree of the applied carbonfibers.

The composite material obtained after such electrolytic treatment allowsthe adhesiveness between the carbon fibers and the matrix resin to beoptimized for solving the problem that too strong adhesiveness causesbrittle failure in the composite material and lowers the tensilestrength in the fiber direction, and solving the problem that theadhesiveness to the resin is poor not allowing the strength in thenon-fiber direction to be exhibited though the tensile strength in thefiber direction can be kept high. So, the obtained composite materialcan exhibit well-balanced strength properties in both the fiberdirection and the non-fiber direction.

After completion of such electrolytic treatment, the obtained carbonfibers can be treated with a sizing agent, so that the fibers can bebundled. As the sizing agent, a sizing agent compatible with the matrixresin used in the composite material can be appropriately selected.

The carbon fibers have a high compressive strength and a high strandtensile modulus. Therefore, the carbon fibers can be applied to variousmolding methods such as an autoclave molding method using a prepreg,resin transfer molding method using a preform such as a woven fabric,and filament winding molding method. The carbon fibers are suitable forproducing aircraft members, pressure vessel members, automobile membersand sporting goods members such as fishing rods and golf shafts by usingthese molding methods.

The methods for measuring the respective physical values stated in thisspecification are as follows.

Intrinsic Viscosity

One hundred and fifty milligrams of a polyacrylonitrile-base polymerdried by heat treatment at a temperature of 120° C. for 2 hours isdissolved at a temperature of 60° C. into dimethylformamide containing50 ml of sodium thiocyanate by 0.1 mol/liter. The dropping time of theobtained solution between gage marks is measured at an accuracy of 1/100seconds using an Ostwald viscometer at a temperature of 25° C. Themeasured dropping time is expressed as t (sec). Similarly, the droppingtime of dimethylformamide containing sodium thiocyanate by 0.1 mol/literbut not containing the polyacrylonitrile-base polymer is also measured.The dropping time is expresses as t0 (sec). The intrinsic viscosity [η]is calculated from the following formula:

[η]={(1+1.32×ηsp)^((1/2))−1}/0.198

ηsp=(t/t0)−1.

Meanwhile, in the examples and comparative examples described later, asthe sodium thiocyanate and dimethylformamide, the guaranteed reagentsproduced by Wako Pure Chemical Industries, Ltd. were used.

Melting Point Tm in Wet Heat

The polyacrylonitrile-base polymer to be measured is freeze-ground inliquid nitrogen, and the ground polymer is passed through a sieve having0.5 mm meshes, to obtain a powder of the polymer. Five milligrams of theobtained powder is accurately weighed, to prepare a sample for DSCmeasurement. The prepared sample is sealed in a sealable sample pan forDSC having a pressure resistance of 2 MPa or more, together with 5 mg ofpure water. Then, the sample pan is used to measure DSC at a temperaturerising rate of 10° C./min from room temperature to 220° C., and thetemperature corresponding to the endothermic peak appearing in anapproximate temperatures range from 150 to 200° C. is read as themelting point Tm (° C.) in wet heat.

Meanwhile, in the examples and comparative examples described later, asthe sample pan for DSC, medium pressure pan ME29990 (pressure resistance2 MPa) for DSC produced by Mettler was used, and as the DSC measuringinstrument, DSC3100SA produced by Bruker was used.

Polyacrylonitrile-base Polymer Concentration in Spinning Dope

About 10 g of the spinning dope to be measured is dropped into water,while its size is kept at 2 mm or less, for coagulation. The coagulatedpolymer is washed with running water of 80° C. for 4 hours. The washedpolymer is dried by a hot air dryer at 120° C. for 2 hours. The weightof the spinning dope dropped into water is expressed as A (g), and theweight of the polymer after washing and drying is expressed as B (g).The polyacrylonitrile-base polymer concentration (%) in the spinningdope is obtained from the following formula:

Polyacrylonitrile-base polymer concentration (%) in spinningdope=B/A×100.

Specific Gravity of Stabilized Fibers

The specific gravity of stabilized fibers is measured by a liquiddisplacement method according to the method described in JIS R 7601(1986). As the immersion liquid, ethanol is used without being refined.One point zero to one point five grams of stabilized fibers are sampled,and dried using a hot air dryer at a temperature of 120° C. in air for 2hours. The dry mass A (g) is measured, and the dry fibers are immersedin ethanol having a known specific gravity (specific gravity p), and themass B (g) of the fibers in the ethanol is measured. The specificgravity of the stabilized fibers is obtained from the following formula:

Specific gravity of stabilized fibers=(A×ρ)/(A−B).

Meanwhile, in the examples and comparative examples described later, asthe ethanol, the guaranteed reagent produced by Wako Pure ChemicalIndustries, Ltd. was used.

Specific Gravity of Carbon Fibers

The specific gravity of carbon fibers is measured by a liquiddisplacement method according to the method described in JIS R 7601(1986). As the immersion liquid, orthodichlorobenzene is used withoutbeing refined. One point zero to one point five grams of carbon fibersare sampled, and the weight of the carbon fibers is accurately weighedas fiber mass A (g). In succession, the carbon fibers are immersed inorthodichlorobenzene having a known specific gravity (specific gravityp), and the mass B (g) of the fibers in orthodichlorobenzene ismeasured. The specific gravity of the carbon fibers is obtained from thefollowing formula:

Specific gravity of carbon fibers=(A×ρ)/(A−B).

Meanwhile, in the examples and comparative examples described later, asthe orthodichlorobenzene, the guaranteed reagent produced by Wako PureChemical Industries, Ltd. was used.

Strand Tensile Modulus of Carbon Fibers

The strand tensile modulus of carbon fibers is obtained according to JISR 7601 (1986) “Resin Impregnated Strand Test Methods.” In this case, theresin impregnated strand of the carbon fibers to be measured is preparedby impregnating the carbon fibers with 100 parts by weight of3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane-carboxylate, 3 parts byweight of boron trifluoride monomethylamine and 4 parts by weight ofacetone, and heat-treating at a temperature of 130° C. for 30 minutes,for curing. Further, six strands are measured, and the arithmetic meanvalue of the measured values is employed as the strand tensile modulusof the carbon fibers.

Meanwhile, in the examples and comparative examples described later, asthe 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane-carboxyl ate,“BAKELITE” (registered trademark) ERL4221 produced by Union Carbide wasused.

Conduction Electron Density of Carbon Fibers by ESR

The carbon fibers to be determined are accurately weighed, and an ESRinstrument is used to determine the signal of near g=2.002 at therespective temperatures shown in the following conditions:

-   -   Center field: Near 3377 G    -   Sweep width: 200 G    -   Modulation: 100 kHz, 2 G    -   Microwave: 9.46 GHz, 1 mW    -   Sweep time: 83.886 seconds x 4 times    -   Time constant: 327.68 ms    -   Number of data points: 1024    -   Measuring temperatures: 10, 50, 100, 150, 200, 250 and 296 K.

The spectrum of the obtained differential curve is integrated twice tocalculate the signal intensity. The signal intensity is converted intothe number of spins per weight, using a standard sample having a knownnumber of spins per weight (for example, an ion implanted polyethylenefilm, the number of spins of which is determined using copper sulfatepentahydrate as a standard sample). With the obtained number of spinsper weight at each temperature as y and the inverse number of theabsolute temperature of the measuring temperature as x, coefficients aand b are obtained base on the linear formula of y=ax+b by the leastsquare method, and the coefficient b as the number of spins is employedas the conduction electron density (spins/g).

Meanwhile, in the examples and comparative examples described later, ESRInstrument ESP350E produced by Bruker was used as the ESR instrument.

Crystal Size of Carbon Fibers

The carbon fibers to be determined are aligned and fixed using collodionalcohol solution, to prepare a square pole test sample having a heightof 4 cm and each side length of 1 mm. The prepared test sample isdetermined using a wide angle X-ray diffractometer under the followingconditions:

-   -   X ray source: CuKα ray (tube voltage 40 kV, tube current 30 mA)    -   Detector: Goniometer+Monochrometer+Scintillation counter    -   Scanning range: 2θ=10 to 40°    -   Scanning mode: Step scan, step interval 0.02°, count time 2        seconds.

In the obtained diffraction pattern, the half value width of the peakappearing near 2θ=25 to 26° is obtained and, based on the value, thecrystal size is calculated from the following Scherrer's formula:

Crystal size (nm)=Kλ/β₀ cosθ_(B)

-   -   where K: 1.0, λ,: 0.15418 nm (wavelength of X ray)

β₀: (β_(E) ²−β₁ ²)^(1/2)

β_(E): Apparent half value width (measured value) rad

β₁: 1.046×10⁻² rad

-   -   θB: Bragg diffraction angle.

Meanwhile, in the examples and comparative examples described later,XRD-6100 produced by Shimadzu Corporation was used as the wide angle Xray diffractometer.

Average Single Filament Diameter of Carbon Fibers

Of the carbon fiber bundle comprising numerous carbon filaments to bemeasured, the weight A (g/m) per unit length and the specific gravity B(g/cm³) are obtained. With the number of filaments of the carbon fiberbundle to be measured as C, the average single filament diameter (pm) ofthe carbon fibers is calculated from the following formula:

Average single filament diameter of carbon fibers(μm)=((A/B/C)/π)^((1/2))×2×10³.

Measurement of Composite Compressive Strength

The following raw resins are mixed and stirred for 30 minutes to obtaina resin composition:

-   -   Bisphenol A diglycidyl ether resin: 30 wt %    -   Bisphenol A diglycidyl ether resin: 30 wt %    -   Phenol novolak polyglycidyl ether resin: 27 wt %    -   Polyvinyl formal resin: 5 wt %    -   Dicyandiamide: 4 wt %    -   3-(3,4-dichlorophenyl)-1,1-dimethylurea: 4 wt %.

Next, a release paper sheet coated with silicone is coated on thesilicone surface with the obtained resin composition, to prepare a resinfilm. The prepared resin film is wound around the surface of a steeldrum having a circumference of about 2.7 m and controlled in atemperature range from 60 to 70° C. with the resin composition surfacekept outside.

Then, a carbon fiber bundle unwound from a creel is traversed on thesurface of the resin composition wound around the steel drum, forarrangement. Further, it is covered with another identical resin filmwith the resin composition surface kept downward, and a rollpre-arranged separately is kept in rolling pressure contact with thesurface of the outside resin film, for impregnating the resin into thefiber bundle, to prepare a unidirectional prepreg having a width of 300mm and a length of 2.7 m. The fiber areal weight of the prepreg isadjusted to be 190 to 200 g/m² by changing the rotational speed of thedrum and the traverse feed rate.

Multiple sheets of the obtained prepreg are laminated with the fiberdirections kept in one direction, and treated at a temperature of 130°C. at a pressure of 0.3 MPa for 2 hours, to cure the resin, for forminga 1 nun thick laminated sheet (fiber reinforced composite material).From the laminated sheet, specimens having a thickness of 1±0.1 mm, awidth of 12.7±0.13 mm, a length of 80±0.013 mm and a gauge portionlength of 5±0.13 mm are cut out. Meanwhile, at both the ends (37.5 mmeach from both the ends) of each specimen, a reinforcing sheet is fixedby an adhesive, etc. to have a gauge portion length of 5±0.13 mm.

According to ASTM D695 (1996), six specimens (n=6) are tested to measurethe compressive strength values at a strain rate of 1.27 mm/min, and theobtained compressive strength values are converted into, those of afiber volume fraction of 60%. The mean value is employed as thecomposite compressive strength.

Meanwhile, in the examples and comparative examples described later,“Epikote” (registered trademark) 1001 produced by Japan Epoxy ResinsCo., Ltd. was used as the bisphenol A diglycidyl ether resin, “Epikote”(registered trademark) 828 produced by Japan Epoxy Resins Co., Ltd., asthe bisphenol A diglycidyl ether resin, “Epiclon” (registeredtrademark)-N740 produced by Dainippon Ink and Chemicals, Inc., as thephenol novolak polyglycidyl ether resin, “Vinylec” (registeredtrademark) K produced by Chisso Corporation, as the polyvinyl formalresin, DICY7 produced by Japan Epoxy Resins Co., Ltd. as thedicyandiamide, and DCMU-99 (curing agent) produced by Hodogaya ChemicalCo., Ltd.), as the 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

Examples 1 to 8 and Comparative Example 1 to 8 described below used therespective conditions of the respective examples and the respectivecomparative examples stated in Tables 1 and 2 based on the methoddescribed in the following comprehensive example.

Comprehensive Example

Acrylonitrile and the copolymerized amount (mol %) of the comonomershown in Table I were copolymerized by radical polymerization usingdimethyl sulfoxide as a solvent and an azo-base compound as aninitiator, to produce a polyacrylonitrile-base copolymer having anintrinsic viscosity shown in Table 1 (hereinafter may be merely called apolyacrylonitrile-base copolymer). The melting point Tm (° C.) in wetheat of the produced polyacrylonitrile-base polymer was measured. Themeasured result is shown in Table 1.

The polymer concentration was adjusted to ensure that the polymerconcentration (wt %) of the obtained polyacrylonitrile-base polymer inthe spinning dope prepared described below might achieve the value shownin Table 1, and subsequently ammonia gas was blown in to neutralizeitaconic acid and to introduce ammonium groups into thepolyacrylonitrile-base copolymer, till the pH became 8.5, for preparingthe spinning dope.

The obtained spinning dope was passed through a filter having 0.5 μmmeshes, and with the temperature of the spinning dope kept at 40° C.,the spinning dope was extruded once into air from a spinneret having6,000 extrusion holes, being allowed to pass through air of about 3 mm,and it was introduced into a coagulation bath comprising 20 wt %dimethyl sulfoxide aqueous solution controlled at a temperature of 3°C., to produce a coagulated fiber bundle. In this case, the extrusionamount of the spinning dope was set to achieve the linear extrusion rate(m/min) shown in Table 1. The obtained fiber bundle was washed withwater according to a conventional method and drawn in hot water to 3.5times, and had an amino modified silicone oil deposited on it.

The obtained drawn fiber bundle was run in contact with a roller heatedto a temperature of 170° C., for drying heat treatment. Then, it wasdrawn to 3.7 times in a pressure steam with its temperature kept in arange from 150 to 190° C., to obtain polyacrylonitrile-base precursorfibers comprising 6,000 filaments drawn at a total drawn ratio of 13times, having a single filament fineness of 0.73 dtex. The intrinsicviscosity and the melting point (° C.) in wet heat of the obtainedpolyacrylonitrile-base precursor fibers were measured. The measuredresults are shown in Table 1.

Then, four sets of the obtained polyacrylonitrile-base precursor fiberswere joined to prepare a precursor fiber bundle comprising 24,000filaments in total for production of carbon fibers. The precursor fiberbundle was treated for stabilization in air with its temperature kept ina range from 240 to. 260° C. while being drawn at a draw ratio of 1.0,to obtain a stabilized fiber bundle having a specific gravity of 1.35.The obtained stabilized fiber bundle was treated for preliminarycarbonization in nitrogen atmosphere with its temperature kept in arange from 300 to 700° C. while being drawn at a draw ratio of 1.15, toobtain a preliminarily carbonized fiber bundle.

The obtained preliminarily carbonized fiber bundle was drawn with thedraw ratio raised from 0.960 in steps of 0.001 in nitrogen atmospherewith 1,500° C. as the highest temperature, and the highest draw ratio atwhich no fiber breakage occurred, namely, the critical draw ratio forcarbonization shown in Table 2 was identified. At the critical drawratio for carbonization, the preliminarily carbonized fiber bundle wastreated for carbonization to obtain a carbon fiber bundle.

Example 1

The conditions stated in the row of Example 1 in Tables 1 and 2 wereemployed in the comprehensive example, to produce a carbon fiber bundle.The strand tensile modulus (GPa), conduction electron density (spins/g),specific gravity, average single filament diameter (pm), crystal size(nm) and composite compressive strength (MPa) of the obtained carbonfiber bundle were measured. The measured results are shown in Table 2.

Example 2

The conditions stated in the row of Example 2 in Tables 1 and 2 wereemployed in the comprehensive example, to produce a carbon fiber bundle.The strand tensile modulus (GPa), conduction electron density (spins/g),specific gravity, average single filament diameter (μm), crystal size(nm) and composite compressive strength (MPa) of the obtained carbonfiber bundle were measured. The measured results are shown in Table 2.

Example 3

The conditions stated in the row of Example 3 in Tables 1 and 2 wereemployed in the comprehensive example, to produce a carbon fiber bundle.The strand tensile modulus (GPa), conduction electron density (spins/g),specific gravity, average single filament diameter (μm), crystal size(nm) and composite compressive strength (MPa) of the obtained carbonfiber bundle were measured. The measured results are shown in Table 2.

Example 4

The conditions stated in the row of Example 4 in Tables 1 and 2 wereemployed in the comprehensive example, to produce a carbon fiber bundle.The strand tensile modulus (GPa), conduction electron density (spins/g),specific gravity, average single filament diameter (1m), crystal size(nm) and composite compressive strength (MPa) of the obtained carbonfiber bundle were measured. The measured results are shown in Table 2.

Example 5

The conditions stated in the row of Example 5 in Tables 1 and 2 wereemployed in the comprehensive example, to produce a carbon fiber bundle.The strand tensile modulus (GPa), conduction electron density (spins/g),specific gravity, average single filament diameter (μm), crystal size(nm) and composite compressive strength (MPa) of the obtained carbonfiber bundle were measured. The measured results are shown in Table 2.

Comparative Example 1

Spinning and drawing were performed as described in Example 2, exceptthat the linear extrusion rate was 1 m/min. However, fiber breakageoccurred frequently in the coagulation step, and stable spinning anddrawing could not be performed.

Example 6

Spinning, drawing, stabilizing-carbonizing treatment and evaluation wereperformed as described in Example 2, except that the linear extrusionrate was 3 m/min. The obtained results are shown in Tables 1 and 2. Itwas found that when the linear extrusion rate was low, the critical drawratio for carbonization of the preliminarily carbonized fibers obtainedby spinning and stabilizing-carbonizing treatment was high, and thestrand tensile modulus and the composite compressive strength of theobtained carbon fibers were also high.

Example 7

Spinning, drawing, stabilizing-carbonizing treatment and evaluation wereperformed as described in Example 2, except that the linear extrusionrate was 12 m/min. The obtained results are shown in Tables 1 and 2.

Comparative Example 2

Spinning, drawing, stabilizing-carbonizing treatment and evaluation wereperformed as described in Example 2, except that the linear extrusionrate was 16 m/min. The obtained results are shown in Tables 1 and 2. Itwas found that when the linear extrusion rate was high, the criticaldraw ratio for carbonization of the preliminarily carbonized fibersobtained by spinning and stabilizing-carbonizing treatment was low, andthe strand tensile modulus and the composite compressive strength of theobtained carbon fibers were also low.

Comparative Example 3

The conditions stated in the row of Comparative Example 3 in Tables 1and 2 were employed in the comprehensive example, to produce a carbonfiber bundle. The strand tensile modulus (GPa), conduction electrondensity (spins/g), specific gravity, average single filament diameter(μm), crystal size (nm) and composite compressive strength (MPa) of theobtained carbon fiber bundle were measured. The measured results areshown in Table 2.

Comparative Example 4

The conditions stated in the row of Comparative Example 4 in Tables 1and 2 were employed in the comprehensive example, to produce a carbonfiber bundle. The strand tensile modulus (GPa), conduction electrondensity (spins/g), specific. gravity, average single filament diameter(μm), crystal size (nm) and composite compressive strength (MPa) of theobtained carbon fiber bundle were measured. The measured results areshown in Table 2.

Comparative Example 5

The conditions stated in the row of Comparative Example 5 in Tables 1and 2 were employed in the comprehensive example, to produce a carbonfiber bundle. The strand tensile modulus (GPa), conduction electrondensity (spins/g), specific gravity, average single filament diameter(μm), crystal size (nm) and composite compressive strength (MPa) of theobtained carbon fiber bundle were measured. The measured results areshown in Table 2.

Comparative Example 6

Spinning and drawing were performed as described in Comparative Example3, except that the linear extrusion rate was 1 m/min. However, sincefiber breakage occurred frequently in the coagulation step, stablespinning and drawing could not be performed.

Comparative Example 7

Spinning, drawing, stabilizing-carbonizing treatment and evaluation wereperformed as described in Comparative Example 3, except that the linearextrusion rate was set at 3 m/min. The obtained results are shown inTables 1 and 2. It was found that when the intrinsic viscosity of thepolyacrylonitrile-base polymer was low, the critical draw ratio forcarbonization of the preliminarily carbonized fibers obtained byspinning and stabilizing-carbonizing treatment could be enhanced onlyslightly even if the linear extrusion rate was made low.

Comparative Example 8

Spinning, drawing, stabilizing-carbonizing treatment and evaluation wereperformed as described in Comparative Example 3, except that the linearextrusion rate was 12 m/min. The obtained results are shown in Tables 1and 2. It was found that when the intrinsic viscosity of thepolyacrylonitrile-base polymer was low, the critical draw ratio forcarbonization of the preliminarily carbonized fibers obtained byspinning and stabilizing-carbonizing treatment could be changed onlyslightly in the case where the linear extrusion rate was high.

Example 8

Spinning, drawing, stabilizing-carbonizing treatment and evaluation wereperformed as described in Example 2, except that the highest temperatureof the carbonization step was 1,800° C. The obtained results are shownin Tables 1 and 2.

TABLE 1 Comonomer and Melting point copolymerized Intrinsic in wet heatamount (mol %) viscosity (° C.) Example 1 Itaconic acid 2.5 191 0.4 molExample 2 Itaconic acid 2.5 191 0.4 mol Example 3 Itaconic acid 3.5 1920.4 mol Example 4 Itaconic acid 7.0 192 0.4 mol Example 5 Itaconic acid2.5 184 0.4 mol Methyl acrylate 1.0 mol % Comparative Itaconic acid 2.5191 Example 1 0.4 mol Example 6 Itaconic acid 2.5 191 0.4 mol Example 7Itaconic acid 2.5 191 0.4 mol Comparative Itaconic acid 2.5 191 Example2 0.4 mol Comparative Itaconic acid 1.6 191 Example 3 0.4 molComparative Itaconic acid 1.2 191 Example 4 0.4 mol Comparative Itaconicacid 3.5 192 Example 5 0.4 mol Comparative Itaconic acid 1.6 191 Example6 0.4 mol Comparative Itaconic acid 1.6 191 Example 7 0.4 molComparative Itaconic acid 1.6 191 Example 8 0.4 mol Example 8 Itaconicacid 2.5 191 0.4 mol Polymer Liner extrusion concentration (wt %) rate(m/min) Example 1 20 6 Example 2 15 6 Example 3 15 6 Example 4 10 6Example 5 15 6 Comparative 15 1 Example 1 Example 6 15 3 Example 7 15 12Comparative 15 16 Example 2 Comparative 20 6 Example 3 Comparative 25 6Example 4 Comparative 8 6 Example 5 Comparative 20 1 Example 6Comparative 20 3 Example 7 Comparative 20 12 Example 8 Example 8 15 6

TABLE 2 Critical draw ratio Strand tensile conduction for carbon-modulus electron density Specific ization (GPa) (×10¹⁹ spins/g) gravityExample 1 0.997 355 5.8 1.82 Example 2 0.990 347 6.0 1.81 Example 30.104 361 5.7 1.82 Example 4 0.986 341 6.1 1.81 Example 5 0.975 330 6.81.80 Comparative — — — — Example 1 Example 6 0.101 358 5.8 1.81 Example7 0.984 337 6.4 1.81 Comparative 0.969 325 7.1 1.80 Example 2Comparative 0.968 323 7.2 1.80 Example 3 Comparative 0.966 322 7.4 1.80Example 4 Comparative 0.968 324 7.1 1.80 Example 5 Comparative — — — —Example 6 Comparative 0.969 325 7.1 1.81 Example 7 Comparative 0.960 3167.5 1.79 Example 8 Example 8 0.990 367 3.5 1.75 Average single Compositefilament Crystal compressive diameter (μm) size (nm) strength (MPa)Example 1 5.3 2.1 1780 Example 2 5.3 2.0 1730 Example 3 5.3 2.1 1820Example 4 5.4 2.0 1700 Example 5 5.4 2.0 1630 Comparative — — — Example1 Example 6 5.3 2.1 1790 Example 7 5.3 2.0 1680 Comparative 5.4 2.0 1550Example 2 Comparative 5.4 2.0 1560 Example 3 Comparative 5.4 2.0 1520Example 4 Comparative 5.4 2.0 1560 Example 5 Comparative — — — Example 6Comparative 5.4 2.0 1540 Example 7 Comparative 5.4 2.0 1480 Example 8Example 8 5.3 2.3 1520

When the intrinsic viscosity of the polyacrylonitrile-base polymer washigher while the concentration of the polymer in the spinning dope washigher, the critical draw ratio for carbonization of the preliminarilycarbonized fibers obtained by spinning and stabilizing-carbonizingtreatment was higher, and the strand tensile modulus of the obtainedcarbon fibers was also higher. Further, it was found that when theconduction electron density of carbon fibers was lower, the compositecompressive strength was higher even at the same crystal size.Furthermore, it was found that when the melting point in wet heat of thepolyacrylonitrile-base polymer was higher, the composite compressivestrength showed a better result.

INDUSTRIAL APPLICABILITY

High drawing can be performed stably in the stabilizing-carbonizingtreatment step without impairing productivity and processability, andbecause of it, carbon fibers excellent in compressive strength andstrand tensile modulus, and excellent further in tensile strength andgrade can be produced at low cost.

The carbon fibers have a high compressive strength and a high strandtensile modulus. Therefore, the carbon fibers can be applied to variousmolding methods such as an autoclave molding method using a prepreg,resin transfer molding method using a preform such as a woven fabric,and filament winding molding method, and are suitable for producingaircraft members, pressure vessel members, automobile members andsporting goods members such as fishing rods and golf shafts by usingthese molding methods.

1. A process for producing polyacrylonitrile-base precursor fibers forproduction of carbon fibers, which comprises spinning a spinning dopecontaining 10 to 25 wt % of a polyacrylonitrile-base polymer having anintrinsic viscosity of 2.0 to 10.0 by extruding it from a spinneret by awet spinning or dry wet spinning method, drying and heat-treating thefibers obtained in the spinning step, and steam-drawing the fibersobtained, wherein the linear extrusion rate of thepolyacrylonitrile-base polymer from the spinneret is 2 to 15 m/min. 2.The process according to claim 1, wherein the linear extrusion rate is 2to 10 m/min.
 3. The process according to claim 1, wherein the spinningmethod is dry wet spinning.
 4. The process according to claim 1, whereinthe melting point Tm in wet heat of the polyacrylonitrile-base polymeras measured by a differential scanning calorimeter is 186 to 200° C. 5.The process according to claim 1, wherein the polyacrylonitrile-basepolymer is a copolymer containing a component copolymerizable withacrylonitrile, and the amount of the copolymerizable component is 0.1 to0.5 mol %.
 6. The process according to claim 1, wherein the singlefilament fineness of the polyacrylonitrile-base precursor fibers forproduction of carbon fibers is 0.7 to 1.0 dtex.
 7. A process forproducing carbon fibers, comprising stabilizing thepolyacrylonitrile-base precursor fibers for production of carbon fibers,produced by the process for producing polyacrylonitrile-base precursorfibers for production of carbon fibers as set forth in claim 6, in airhaving a temperature of 200 to 300° C., while drawing them at a drawratio of 0.80 to 1.20, preliminarily carbonizing the fibers obtained inan inert atmosphere having a temperature of 300 to 800° C., whiledrawing them at a draw ratio of 1.00 to 1.30, and carbonizing the fibersobtained in an inert atmosphere having a temperature of 1,000 to 2,000°C., while drawing them at a draw ratio of 0.96 to 1.05.
 8. The processaccording to claim 7, wherein the draw ratio during stabilization is0.90 to 1.20; the draw ratio during preliminary carbonization is 1.10 to1.30; and the draw ratio during carbonization is 0.97 to 1.05.